水杨醛席夫碱类荧光探针的结构修饰及性能研究

发布时间：2019-01-01 21:44

【摘要】：金属离子是环境化学、生命和医疗等科学领域的重点研究内容,对水溶液中金属离子的检测更是分析化学的热点研究问题。近年来,金属离子荧光探针因具有选择性好,灵敏度高、反应迅速等特征成为研究热点。水杨醛席夫碱因具有C=N-,-OH结构单元,使其与金属具有良好的配位能力,同时,由于这类分子具有较大共轭体系,也表现出优异的荧光性能。但由于其金属络合物在水相和有机相中较低的溶解度使其作为荧光探针在金属离子检测领域的应用受到限制。本论文的主要工作是对水杨醛分子进行结构修饰,具体为在水杨醛分子中引入油溶性基团,增加其金属络合物在有机溶剂中的溶解度,考察金属配合物的荧光性能及其作为金属离子荧光探针的可能性。本论文主要研究工作如下:从烷基酚出发,经付克氏烷基化反应、甲酰化反应合成出3种水杨醛衍生物5-甲基-3-α,α-二甲基-α-苯基水杨醛(3a)、3,5-二-α,α-二甲基-α-苯基水杨醛(3b)和5-特辛基-3-α,α-二甲基-α-苯基水杨醛(3c);3种水杨醛衍生物分别与邻氨基苯酚缩合,合成了三种具有平面共轭体系结构特点的新型席夫碱荧光探针(4a,4b,4c),3种荧光探针分别与Zn~(2+)、Cu~(2+)、Mn~(2+)、Ni~(2+)、Co~(2+)形成络合物。对所合成的配体及络合物进行了结构表征和荧光性质研究,结果表明,所制备的3种荧光探针对Zn~(2+)表现出良好的识别性能,其中4b与Zn~(2+)络合物的荧光强度是配体的5倍左右,4a和4c分别为2倍和2.5倍左右。与Zn~(2+)相比,Cu~(2+)、Mn~(2+)、Ni~(2+)、Co~(2+)与3种配体形成的络合物荧光强度均低于配体。3a-c分别与三种天然氨基酸发生缩合反应,制备出9种新型L-氨基酸水杨醛席夫碱(7a-i),9种新型L-氨基酸席夫碱分别与Zn~(2+)、Cu~(2+)、Mn~(2+)、Ni~(2+)、Co~(2+)络合生成相应的金属络合物。对所合成的荧光探针及金属络合物进行了结构表征和荧光性质研究,结果表明,9种配体与Zn~(2+)的络合物有较强的荧光发射,络合物的荧光强度是配体的1.5倍以上,其中7f达到10倍左右。与Zn~(2+)相比,Cu~(2+)、Mn~(2+)、Ni~(2+)、Co~(2+)与9种配体形成的络合物荧光强度均低于配体,表明这9种配体作为Zn~(2+)的荧光探针具有极好的选择性。研究了Cu~(2+)、Mn~(2+)、Ni~(2+)、Co~(2+)4种金属离子对7f配体作为荧光探针检测锌离子影响,结果表明Cu~(2+)对7f和Zn~(2+)络合物的荧光发射表现出明显的猝灭作用,而其他离子及其混合物则几乎没有影响。研究了7b与Cu~(2+)偶合物的晶体结构,单晶X-衍射检测显示,该络合物晶体属正交晶系,P21空间群。本文共合成了3种水杨醛衍生物,12种水杨醛席夫碱配体,60种金属络合物,全部为文献未见报道的新化合物。
[Abstract]:Metal ions are the focus of environmental chemistry, life and medical science, and the detection of metal ions in aqueous solution is a hot issue in analytical chemistry. In recent years, metal ion fluorescence probes have become a hot research area because of their good selectivity, high sensitivity and rapid reaction. The Schiff base of salicylidene has good coordination ability with metals because of its Cn- (N-OH-OH) structure unit. At the same time, it also exhibits excellent fluorescence properties because of its large conjugated system. However, its low solubility in aqueous and organic phases limits its application as a fluorescent probe in the field of metal ion detection. The main work of this thesis is to modify the structure of salicylic aldehyde molecules by introducing oil-soluble groups into salicylaldehyde molecules to increase the solubility of its metal complexes in organic solvents. The fluorescence properties of metal complexes and the possibility of using them as metal ion fluorescence probes were investigated. The main work of this thesis is as follows: starting from alkylphenol, three salicylic aldehyde derivatives 5-methyl-3- 伪, 伪 -dimethyl- 伪 -phenylsalicylic aldehyde (3a), 3- (5-di- 伪) -diphenylsalicylaldehyde (3a) were synthesized by formylation of alkylphenol and formylation. 伪 -dimethyl- 伪 -phenylsalicylidene (3b) and 5-tert-octyl-3- 伪, 伪 -dimethyl- 伪 -phenylsalicylaldehyde (3c); Three novel Schiff base fluorescent probes (4aAc) with planar conjugation system were synthesized by condensation of three salicylaldehyde derivatives with o-aminophenol, respectively. Three kinds of fluorescent probes were synthesized with Zn~ (2) and Cu~ (2), respectively. Mn~ (2), Ni~ (2), Co~ (2) form complex. The structure and fluorescence properties of the synthesized ligands and complexes were studied. The results show that the three fluorescent probes have good recognition performance for Zn~ (2). The fluorescence intensity of 4b / Zn~ (2) complexes is about 5 times of that of ligands, and the fluorescence intensities of 4a and 4c complexes are 2 and 2. 5 times, respectively. Compared with Zn~ (2), the fluorescence intensity of Cu~ (2), Mn~ (2), Ni~ (2), Co~ (2) complexes with three ligands was lower than that of ligands. 3a-c condensed with three natural amino acids. Nine novel L-amino acid salicylaldehyde Schiff bases (7a-i) and nine novel L-amino acid Schiff bases were synthesized by complexing with Zn~ (2), Cu~ (2), Mn~ (2), Ni~ (2), Co~ (2) to form corresponding metal complexes. The structure and fluorescence properties of the synthesized fluorescent probes and metal complexes have been studied. The results show that the complexes of 9 ligands with Zn~ (2) have strong fluorescence emission, and the fluorescence intensity of the complexes is more than 1.5 times that of the ligands. Among them, 7 f is about 10 times. Compared with Zn~ (2), the fluorescence intensities of Cu~ (2), Mn~ (2), Ni~ (2), Co~ (2) complexes with 9 ligands were lower than those of ligands, which indicated that these ligands had excellent selectivity as fluorescence probes for Zn~ (2). The effects of four metal ions, Cu~ (2), Mn~ (2), Ni~ (2), Co~ (2), on the detection of zinc ions by using 7f ligands as fluorescence probes were studied. The results show that Cu~ (2) has obvious quenching effect on fluorescence emission of 7f and Zn~ (2) complexes, while other ions and their mixtures have little effect. The crystal structure of the coupling compound 7b with Cu~ (2) has been studied. The X-ray diffraction analysis shows that the complex crystal belongs to the orthogonal crystal system and P21 space group. In this paper, three salicylaldehyde derivatives, 12 salicylaldehyde Schiff base ligands and 60 metal complexes have been synthesized, all of which are new compounds not reported in literature.
【学位授予单位】：哈尔滨理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3

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